Method of developing silver halide photosensitive material

ABSTRACT

A photographic developing process is disclosed which comprises developing an exposed light-sensitive silver halide emulsion layer of a photographic material with an alkaline solution in the presence of hydroquinone and a derivative of p-aminophenol having the general formula   WHEREIN EACH OF X and Y is selected from the group consisting of a hydrogen atom, an alkyl group having one to four carbon atoms or an alkoxy group, Z is selected from the group consisting of an alkyl group having one to four carbon atoms and an alkoxy group, and each of R1 and R2 is an alkyl group having one to four carbon atoms.

United States Patent [191 Arai et al.

[111 3,801,323 [451 Apr. 2, 1974 METHOD OF DEVELOPING SILVER I-IALIDE PIIOTOSENSITIVE MATERIAL Primary ExaminerJ. Travis Brown Assistant Examiner-M. F. Kelley Attorney, Agent, or Firm-Sughrue, Rothwell, Mion,

[75] Inventors: Atsuaki Arai; Kinji Ohkubo;

Tatsuya Tajima; Mitsugu Tanaka; Zmn & Macpeak Yoshinori Tsuchiya, all of Kanagawa, Japan [57] ABSTRACT [73] Assignee: Fuji Photo Film Co., Ltd., A photographic developing process is disclosed which Kanagawa, Japan comprises developing an exposed light-sensitive silver halide emulsion layer of a photographic material with [22] Flled 1971 an alkaline solution in the presence of hydroquinone [21] App]. No.: 192,952 and a derivative of p-aminophenol having the general formula [30] Foreign Application Priority Data Oct. 27, 1970 Japan 45-94882 R Y X [52] U.S. Cl 96/66 R, 96/66.3, 96/95,

96/22 ux 1 V [51] Int. Cl G030 5/30, G03c 1/06 [58] Field of Search 96/66, 95, 55, 29, 66.3, wherein each of X and Y is Selected from the g p consisting of a hydrogen atom, an alkyl group having [56] References Cited one to four carbon atoms or an alkoxy group, Z is selected from the group consisting of an alkyl group UNITED STATES PATENTS having one to four carbon atoms and an alkoxy group, 3,134,673 5/1964 Ganguin 96/66 and ach of R and R is an alkyl group having one to 3,265,499 8/1966 Willems 96/66 f carbon atoms 3,600,176 8/1971 Haist 96/66 19 Claims, 1 Drawing Figure t: w E: O 0.5

TIME OF DEVELOPMENT (3E0) PAIENTEDAPR 219M SL801; 323

TIME OF DEVELOPMENT (SEO) METHOD OF DEVELOPING SILVER HALIDE PHOTOSENSITIVE MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for devel- 2. Prior Art Photosensitive materials have heretofore been prepared by coating a photosensitive silver halide emulsion on a substrate such as a glass plate, paper, plastic films etc., and then followed by drying the coated product. After the thus prepared photosensitive materials have been exposed to light, they are developed in a developer liquid which is an alkaline aqueous solution containing a developing agent as its essential ingredient and thereafter sequentially subjected to stopping, fixation and water-rinsing treatments. However, since these series of treatment processes require a long period of time, many proposals have been made so as to shorten the processing time, Examples of such improved methods include high temperature processing, single-bath development and fixation, double bath stabilization treatment process, etc. One of the currently employed methods for shortening the time of development comprises adding a developing agent into a silver halide emulsion layer and then treating the layer with a highly alkaline aqueous solution containing such photographic additives as alkali agents, antioxidants, retarders, and the like. The characteristic feature of this method resides in making quick development possible with a shortened developing reaction time which is due to the use of highly increased pH of the processing liquid that can be only attained in the absence of a developing agent in the processing liquid so as not to degrade its storability properties. The silver halide photosensitive material to be suitably employed in this method include silver chloride emulsions and silver chlorobromide emulsions having low silver bromide content and which have a high rate of developing reaction.

On the other hand, various attempts have been made to carry out similar quick processing even with silver chlorobromide emulsions having a high silver bromide content, pure silver bromide emulsions and silver iodobromide emulsions by adding to these emulsions a developing agent. However, each of the silver chlorobromide emulsions, pure silver bromide emulsions and silver iodobromide emulsions have slower developing reaction rates than the silver chloride emulsions, so that satisfactory desirable photograph picture chracteristics cannot be obtained in short periods of time.

It is well known in the art that excellent picture characteristics which have never been attainable with the use of hydroquinone alone can be obtained in the usual development process of silver halide photosensitive emulsions containing no developing agent by using a developer liquid containing hydroquinone and a developing agent having super additivity such as l-phenyl 3- pyrazolidone or N-methyl-p-aminophenol (known as P or MQ developing liquids). Additionally, it is disclosed in U.S. Pat. No. 2,751,297 thatthe rate of development is accelerated by the addition of l-phenyl-3- pyrazolidone to a single hydroquinone solution or to an MO developer.

By utilizing these prior teachings, we have made an attempt to accelerate the quick development of silver chlorobromide emulsions, silver bromide emulsions and silver iodobromide emulsions each containing a developing agent admixed therein. It was found, however, that the addition of these accelerators, i.e., l-phenyl-3- pyrazolidone, N-methyl-p-aminophenol, etc., to the emulsion is disadvantageous because these accelerator compounds have a tendency to undergo oxidation which not only results in lowering the activity of the compound during the storage of the sample but also discolors or contaminates the substrate base.

It has also been reported that certain p-aminophenol derivatives such as Compound (I) shown below, which is disclosed in Japanese Pat. Publication No. 37-5993, and Compound (II) shown below, which is disclosed in US. Pat. No. 3,265,499, have more excellent super additive powers than the above-mentioned l-phenyl-3- pyrazolidone and N-methyl-p-aminophenol when they are used in combination with hydroquinone.

It is disclosed in British Pat. No. 1,126,219 that Compounds (III) and (IV) shown below, have superior developing performance when they are used in an alkali developer solution containing a silver halide for diffusiontranscrip tion use.

We have also tried to add these compounds to a photographic emulsion, but with unsuccessful results since when these compounds are incorporated into the emulsion the emulsion is very susceptible to fogging as well as to contamination due to the oxidation of the developing agent even after known fog inhibitors and antioxidants have been added to the emulsion. Compounds I IV are shown below:

wherein R, is typically an alkyl group having one to six carbon atoms, R is typically a methyl or ethyl group and X is typically a methyl, ethyl, or alkoxy group having one to six carbon atoms;

ca om wherein each of X and X is typically a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyl amino group, etc.;

x Y R /N --OH H I z (III) wherein R is a hydrogen atom or an alkyl group containing one to five carbon atoms and X, Y and Z are methyl groups; and

X Y R N-- OH Z (IV) wherein R is a hydrogen atom or an alkyl group con taining one to five carbon atoms and X, Y and Z are methyl groups.

Objects of the Invention A primary object of this invention is to improve the photographic characteristics in a conventional rapid developing process of photographic paper, by adding compounds of the general Formula (V) shown below,

into silver halide emulsion layers, protective layers or 15 undercoating layers containing a developing agent therein.

DETAILED DESCRIPTION OF THE INVENTION Compound tov To Amount per Mole of Light Proportion be Added Sensitive Silver Halide Therebctween or per Liter of Alkaline by Weight Solution Hydroquinone Layer 5 to 500 grams 1 Compound Layer 0.05 to 50 grams l/l()0 to Hydroquinone Layer 5 to 500 grams Co mpound Solution 0.0] to grams I-Iydrgquinone Solution 1 to 70 grams Compound Layer 0.05 to 50 grams Hydroquinone Solution 1 to 7() grams l Compound Solution 0.01 to 20 grams 1/100 to l/lO wherein X and Y are each hydrogen, alkyl or alkoxy groups containing one to four carbon atoms; Z is an alkyl or alkoxy group containing one to four carbon atoms; and R I and R are each alkyl groups containing one to four carbon atoms.

A second object of this invention is to employ a com pound of the general Formula (V) as an essential developing agent having super additivity when combined with hydroquinone for developing monochromic and color photography.

A further object of this invention is to accelerate the developing speed of the usual developing treatment by adding a compound of the general Formula (V) into the emulsion layer, protective layers or undercoating layers of silver halide photosensitive materials containing no developing agent.

Other objects will be apparent to those skilled in the art as the description of this invention proceeds.

BRIEF DESCRIPTION OF THE INVENTION We have now found that the aforesaid disadvantages can be eliminated by the addition to a silver halide photographic emulsion of a compound represented by the general Formula (V) in combination with hydroquinone and also that excellent photographic characteristics can then be obtained by developing the photographic material with a single hydroquinone developer. We have also discovered that an alkaline developer liquid containing the compound represented by the general Formula (V) and hydroquinone is an excellent photographic liquid developer.

The hydroquinone can be incorporated in the emulsion layer and/or a layer adjacent thereto, and the derivative can be incorporated in the alkaline solution. The hydroquinone can also be incorporated in the alkaline solution and the derivative incorporated in the emulsion layer and/or a layer adjacent thereto. Finally, the hydroquinone and the derivative can be incorporated in the emulsion layer or a layer adjacent thereto or the hydroquinone and the derivative incorporated in the alkaline solution.

The compound represented by the general Formula (V) is effective for the combination with either pure silver chloride, silver chlorobromide, pure silver bromide or silver iodobromide emulsions, but an outstanding effect is obtained when it is combined with silver chlorobromide, pure silver bromide or silver iodobromide emulsions, each of which is known to have a slow developing speed.

The developing agents to be used in combination with the compounds of the general Formula (V) in accordance with the present invention are not limited to any specific type and it is possible to use any compounds which are conventionally employed as photographic developing agents having reducing activity. Examples of such developing agents include hydroquinone or its derivatives, catechol or its derivatives, ascorbic acid, and the like.

The substrate to be used for supporting the silver halide photographic material may be any base material so far as it can support a silver halide emulsion layer, and typically includes paper, plastic films, etc., which may be further provided with a baryta layer or an undercoating layer.

The silver halide emulsion to be used is to be understood to include silver halide photosensitive materials, and may contain gelatin or other synthetic resins such as poly(vinyl alcohol), poly(viny1 acetal), etc., as a binder.

Since the compounds represented by the general Formula (V) are novel compounds, the method for the preparation of several particular compounds will be explained in detail.

"SYNTHESIS EXAMPLE 1 Synthesis of 4-dimethy1amino-2,3,5-trimethy1pheno1 pressed with hydrogen to the hydrogen pressure of 35- atm., then stirred at room temperature for 24 hours. After filtering the reaction product mixture, ethanol was removed from the filtrate by distillation under reduced pressure, and the residue was further distilled under the reduced pressure of 1 mmHg in an oil bath. Then the temperature of the oil bath was raised to 170C., and the distillate collected and dissolved in about 500 ml. of ether. By introducing dry hydrogen chloride gas into the ether solution, 13.5g (yield of 50.0 percent) of the desired compound was obtained as white powdery crystals, which were recrystallized from a solvent mixture of dilute hydrochloric acid and ethanol to give sublimative colorless crystals.

SYNTHESIS EXAMPLE 2 Synthesis of 4-dimethy1amino-3,S-dimethyl-phenol hydrochloride A 500 m1. autoclave was charged with 24g of 4-amino-3,S-dimethylphenol, which was prepared according to the method described in Rowe, Bannister, Storey, J. Soc. Chem. Ind. 50, 79, (1931), 37.6 ml; of 37 percent aqueous formalin solution, 2.0g of Pd-C and 300 ml. of ethanol, compressed with hydrogen to the hydrogen pressure of 70 atm., then stirred at room temperature for about 24 hours. After filtering the reaction product, the filtrate was distilled under reduced pressure in an oil bath and the residue was further distilled under reduced pressure of 1 mmHg. After raising the oil bath temperature to 170C, the distillate was recovered, dissolved in about 500 m1. of ether followed by introducing to the resulted solution dry hydrogen chloride gas to give 16.8g (yield of 47.3 percent) of white powdery crystal of the desired compound. Recrystallization of this compound from ethanol gave sublimative colorless crystals.

SYNTHESIS EXAMPLE 3 Synthesis of 4-dimethy1amino-3,S-dimethoxy-phenol hydrochloride in accordance with a conventional method (e.g., Jikken Kagaku Koza, 17, (A), pp. 509), 3,5- dimethoxyphenol was coupled with diazonium salt of sulfanylic acid to form an azo dye which was then reduced with sodium hydrosulfite to give 4-amino-3,5-

dimethoxy-phenol. By using 20g of 4-amino-3,5- dimethoxy-phenol, 20 m1. of 80 percent aqueous acetaldehyde solution, 2.0g of 10% Pd-C and 300 m1. of ethanol, 14.2g (yield of 45.5 percent) of white powdery crystals of the desired compound was obtained according to the same manner as that described in the above Synthesis Example 1.

The invention will be further explained in detail by the following examples:

EXAMPLE 1.

Several samples of coating solutions were each prepared by adding necessary hardening agents, coating agents, and developing agents shown in Table 1 to 400 cc of silver halide gelatin emulsion containing g gelatin and 20g silver chlorobromide in which the silver bromide was mol% thereof. Photographic baryta paper of l50g/m was coated with each solution and then provided with, under the set state before drying of the coated emulsion, a protective layer consisting of 20}; gelatin, 6 cc 6? saponin (as 6%ir1ethanol solution) and one liter of water, after which it was dried to prepare each sample as designated A to I in Table 1.

The thus prepared photographic paper was exposed through an optical wedge (step wedge) and then developed with an activated solution having a composition as follows:

Sodium sulfite anhydride 45g Sodium hydroxide 48g Potassium bromide 1.3g

Water to make the entire solution to 1,000cc.

After being further stabilized with a stabilizer solution containing ammonium thiocyanate (NH SCN), photographic characteristics were measured. The results are given in Table 1.

TXBLET phenyl)pyrrolidine-HC1 salt 3.3.S-trimethyl-I-aminophenol-HCl salt H g Hydroquinone 064g 4 dimethylamino-2.3,5- trimethyl-phenol HCl salt I lOg Hydroquinone 0.6lg

4-dimethylamino-3.S-dimethylphenol-HCI salt L85 As can be seen from the results in Table 1, Samples H and I, to which the compounds of this invention were incorporated, exhibited outstandingly high values in sensitivity, maximum density and gamma, when compared to the other samples.

EXAMPLE 2 A coating solution was prepared by adding necessary hardening agent and coating additives to 400 cc of silver halide gelatin emulsion containing 50g gelatin and g silver iodobromide containing 1.5 mol percent of silver iodide. Photographic baryta paper of 150 g/m was coated with the above coating solution and further coated, under the set state before drying of the coated emulsion layer, with a coating solution comprising 20g gelatin, 30g of hydroquinone and 1.4g of 4-dimethylamino-Z,3,5-trimethyl phenol hydrochloride as a developing agent, 2g of sodium benzene sulfinate as an antioxidant, 3 cc of 30 percent aqueous formalin solution, 60c of a 6 percent methanol solution of saponin and one liter of water and thereafter dried.

A control sample was similarly prepared without adding 4-dimethylamino-2,3,S-trimethylphenol hydrochloride.

The thus prepared samples were treated according to the manner of Example 1 The samples of this invention exhibited superior values in sensitivity, maximum concentration and gamma to control samples.

EXAMPLE 3.

Photographic baryta paper of 150 g/m was coated with a solution comprising 50g of gelatin, 35g of hydroquinone, 1.4g of 4-dimethylamino-3,S-dimethylphenol hydrochloride, 2g of sodium benzene sulfinate as the antioxidant for hydroquinone, 200 of a 30 percent aqueous formalin solution, 1.0g of fluorescent whitening agent (Blankophor BUP manufactured by Bayer Co., West Germany) and one liter of water. Upon this there was coated a coating solution comprising 400 cc of silver halide gelatin emulsion containing 20g of silver chlorobromide containing 60 mol percent silver bromide and other necessary additives such as hardening agents and coating additives. The thus coated paper was further provided with a protective layer by coating thereon a solution comprising 20g gelatin, 6 cc of 6 percent methanol solution of saponin and one liter of water.

A comparison sample was prepared similarly but without 4-dimethylamino-3,S-dimethylphenol hydrochloride.

Both samples were subjected to treatment as described in Example 1. It was noted that the sample in which 4-dimethylamino-3,S-dimethylphenol was added to the undercoating layer gave results superior to those obtained with the control samples shown by extremely higher sensitivity, maximum density and gamma values.

EXAMPLE 4.

Photographic paper was prepared by coating on photographic baryta paper a coating solution comprising 400 cc of silver halide gelatin emulsion containing 50g gelatin and 20g silver chlorobromide in which the content of the silver bromide was 50 mol percent and necessary hardening agents and coating additives.

The thus prepared paper was developed with the use of a developer liquid having the following composition, and the change in density in relation to the developing period at a constant exposure dosage was plotted in curves shown in FIG. 1.

Curve A Use of hydroquinone alone;

Curve B Combined use of hydroquinone with l-phenyl-3-pyrazolidone;

Curve C Combined use of hydroquinone with metal;

Curve D Combined use of hydroquinone with d-diethylamino-2-methylphenol hydrochloride;

Curve E Combined use of hydroquinone with 4-dimethylaminn-2,3,S-trimethylphenol hydrochloride; and

Curve F Combined use of hydroquinone with 4- dimethylamino-3,S-dimethylphenol hydrochloride.

EXAMPLE 5 Photographic baryta paper of 150 g/m was coated with a coating solution prepared by adding 30g hydroquinone and other requisite additives per one Kg of a silver halide emulsion containing 40g of silver chlorobromide (60 mol percent silver bromide) per g gelatin and then dried. The thus prepared photographic paper was exposed to light through a step wedge, then developed for 4 seconds with the activated solution used in Example 1 and thereafter stabilized with a sta- Y X bilizer solution containing ammonium thiocyanate. For comparison, the same treatment was carried out using an activator solution containing 0.9g per liter of the R, compound of Synthesis Example 1. The results ob- 5 Z tained after measuring specific sensitivity, maximum wherein each of X and Y is selected from the group density and gamma are given in Table 2. consisting of a hydrogen atom, an alkyl group having As seen from Table 2, thecon po und of Synthesis E xone to four carbon atoms or an alkoxy group, Z is seample reasy accelerated the development process. lected from the group consisting of an alkyl group hav- TABLE 2 V Specific Maximum Sensitivity Density Gamma Activated solution containing no compound of Synthesis Example (1) 1.00 1.05 1.51 Activated solution containing the compound of Synthesis Example (1) 1.42 1.30 1.90

EXAMPLE 6 ing one to four carbon atoms and an alkoxy group, and

each of R and R is an alkyl group having one to four carbon atoms.

2. The photographic developing process according to claim 1, wherein said hydroquinone is incorporated in said emulsion layer, in an adjacent layer to said emulsion layer or in said emulsion layer and an adjacent layer to said emulsion layer, and said derivative is incorporated in said alkaline solution.

3. A photographic developing process according to claim 1, wherein said hydroquinone is incorporated in said alkaline solution, and said derivative is incorporatedin said emulsion layer, in an adjacent layer to said Photographic baryta paper of 1.50 g/m was coated with a solution containing 1.8g of the compound of Synthesis Example 2 and other requisite additives per kg of the silver halide emulsion used in Example 5 and then dried to give a photographic paper. Another photographic paper was similarly prepared but using an emulsion containing no compound of Synthesis Example 2. Each photographic paper sample was exposed to light through a step wedge, then developed for 4 seconds with an activated solution of Example 1 containing 20g of hydroquinone per liter of the solution, thereafter stabilized with a stabilizing solution containing. ammonium rhodanate. Results of the test for specific sensitivity, maximum density andv gamma are given in cent layer to Sam emulslon layer 4. A photographic developing process according to Table 3.

claim 1, wherein said hydroquinone and said derlvatlve TABLE 3 are incorporated in said emulsion layer, in an adjacent 4O layer to said emulsion layer or in said emulsion layer Specific Maximum and an adjacent layer to said emulsion layer. Sensmmy Density Gamma S. A photographic developing process according to I claim 1, wherein said hydroquinone and said derivative 31%;;frpeiggigtia mnptiecpg ound L00 M8 030 are incorporated in said alkal ne solutlon.

6. A photographic developing process according to Paper containing compound claim 2, wherein the amount of said hydroquinone is of symhws Example (2) from 5 to 500 grams per mole of light-sensitive silver halide.

It will be noted from this result that the addition of 7. A photographic developing process according to the compound of Synthesis Example 2 greatly proclaim 4, wherein the amount of said hydroquinone is motes the development of hydroquinone. from 5 to 500 grams per mole of light-sensitive silver As having been set forth in detail, the present invenhalide. tion is not only adaptable for silver halide photosensi- 8. A photographic developing process according to tive materials containing a developing agent in the claim 3, wherein the amount of said derivative is from emulsion layer thereof, but also is quite similarly appli- 55 0,05 to 50 grams per ole f li hp itive Silver h lcable with good results to conventionally used silver ide.

halide photosensitive materials for photographic or 9. A photographic developing process according to copying use containing no developing agent in the claim 4, wherein the amount of said derivative is from emulsion layer thereof. 0.05 to 50 grams per mole of light-sensitive silver hal- What we claim is: ide.

1. A photographic developing process which com- 10. A photographic developing process according to prises developing an exposed light-sensitive silver halclaim 3, wherein the amount of said hydroquinone is ide emulsion layer of a multilayer photographic elefrom I to 70 grams per liter of said alkaline solution. ment with an alkaline solution, hydroquinone and a de- 11. A photographic developing process accordingto 35 emulsion layer or in said emulsion layer and an adja-v rivative of p-aminophenol having the general formula: claim 5, wherein the amount of said hydroquinone is from 1 to 70 grams per liter of said alkaline solution.

12. A photographic developing process according to claim 2, wherein the amount of said derivative is from 0.01 to grams per liter of said alkaline solution.

13. A photographic developing process according to claim 5, wherein the amount of said derivative is from 0.01 to 20 grams per liter of said alkaline solution.

14. A photographic developing process according to claim 1, wherein said derivative is selected from the group consisting of 4-diethylamino-3-ethylphenol hydrochloride; 4-(N-ethyl-N-n-propylamino)-3-nbuthoxy phenol hydrochloride; 4-di-n-propylamino- 2,5-dimethylphenol sulfate; and 4-di-n-butylamino-2,5- dimethylphenol sulfate.

15. A photographic material having at least one lightsensitive silver halide emulsion layer, said material containing hydroquinone and from 0.05 to 50 grams per mole of said silver halide of a derivative of paminophenol having the general formula wherein each of X and Y is selected from the group consisting of a hydrogen atom, an alkyl group having one to four carbon atoms and an alkoxyl group, Z is selected from the group consisting of an alkyl group having one to four carbon atoms or an alkoxy group, and each of R, and R is an alkyl group having one to four carbon atoms.

16. An alkaline solution for photographic development, which contains hydroquinone and from 0.01 to 20 grams per liter of said solution of a derivative of paminophenol having the general formula wherein each of X and Y is selected from the group consisting of a hydrogen atom, an alkyl group having one to four carbon atoms and an alkoxy group, Z is selected from the group consisting of an alkyl group having one to four carbon atoms or an alkoxy group, and each of R, and R is an alkyl group having one to four carbon atoms.

17. The photographic developing process according to claim 1, wherein said hydroquinone is incorporated in any one of said emulsion layer, a protective layer adjacent to said emulsion layer, or an undercoat layer adjacent to said emulsion layer, and said derivative is incorporated in said alkaline solution.

18. The photographic developing process according to claim 1, wherein said hydroquinone is incorporated in said alkaline solution, and said derivative is incorporated in any one of said emulsion layer, a protective layer adjacent to said emulsion layer, or an undercoat layer adjacent to said emulsion layer.

19. A photographic developing process according to claim 1, wherein said hydroquinone and said derivative are incorporated in any one of said emulsion layer, a protective layer adjacent to said emulsion layer, or an undercoat layer adjacent to said emulsion layer. 

2. The photographic developing process according to claim 1, wherein said hydroquinone is incorporated in said emulsion layer, in an adjacent layer to said emulsion layer or in said emulsion layer and an adjacent layer to said emulsion layer, and said derivative is incorporated in said alkaline solution.
 3. A photographic developing process according to claim 1, wherein said hydroquinone is incorporated in said alkaline solution, and said derivative is incorporated in said emulsion layer, in an adjacent layer to said emulsion layer or in said emulsion layer and an adjacent layer to said emulsion layer.
 4. A photographic developing process according to claim 1, wherein said hydroquinone and said derivative are incorporated in said emulsion layer, in an adjacent layer to said emulsion layer or in said emulsion layer and an adjacent layer to said emulsion layer.
 5. A photographic developing process according to claim 1, wherein said hydroquinone and said derivative are incorporated in said alkaline solution.
 6. A photographic developing process according to claim 2, wherein the amount of said hydroquinone is from 5 to 500 grams per mole of light-sensitive silver halide.
 7. A photographic developing process according to claim 4, wherein the amount of said hydroquinone is from 5 to 500 grams per mole of light-sensitive silver halide.
 8. A photographic developing process according to claim 3, wherein the amount of said derivative iS from 0.05 to 50 grams per mole of light-sensitive silver halide.
 9. A photographic developing process according to claim 4, wherein the amount of said derivative is from 0.05 to 50 grams per mole of light-sensitive silver halide.
 10. A photographic developing process according to claim 3, wherein the amount of said hydroquinone is from 1 to 70 grams per liter of said alkaline solution.
 11. A photographic developing process according to claim 5, wherein the amount of said hydroquinone is from 1 to 70 grams per liter of said alkaline solution.
 12. A photographic developing process according to claim 2, wherein the amount of said derivative is from 0.01 to 20 grams per liter of said alkaline solution.
 13. A photographic developing process according to claim 5, wherein the amount of said derivative is from 0.01 to 20 grams per liter of said alkaline solution.
 14. A photographic developing process according to claim 1, wherein said derivative is selected from the group consisting of 4-diethylamino-3-ethylphenol hydrochloride; 4-(N-ethyl-N-n-propylamino)-3-n-buthoxy phenol hydrochloride; 4-di-n-propylamino-2,5-dimethylphenol sulfate; and 4-di-n-butylamino-2, 5-dimethylphenol sulfate.
 15. A photographic material having at least one light-sensitive silver halide emulsion layer, said material containing hydroquinone and from 0.05 to 50 grams per mole of said silver halide of a derivative of p-aminophenol having the general formula
 16. An alkaline solution for photographic development, which contains hydroquinone and from 0.01 to 20 grams per liter of said solution of a derivative of p-aminophenol having the general formula
 17. The photographic developing process according to claim 1, wherein said hydroquinone is incorporated in any one of said emulsion layer, a protective layer adjacent to said emulsion layer, or an undercoat layer adjacent to said emulsion layer, and said derivative is incorporated in said alkaline solution.
 18. The photographic developing process according to claim 1, wherein said hydroquinone is incorporated in said alkaline solution, and said derivative is incorporated in any one of said emulsion layer, a protective layer adjacent to said emulsion layer, or an undercoat layer adjacent to said emulsion layer.
 19. A photographic developing process according to claim 1, wherein said hydroquinone and said derivative are incorporated in any one of said emulsion layer, a protective layer adjacent to said emulsion layer, or an undercoat layer adjacent to said emulsion layer. 